Pesticidal preparations and method thereof



United States Patent Office 3,484,526 Patented Dec. 16, 1969 US. Cl. 424-300 4 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to pesticidal preparations having an increased activity, containing mixtures of carbamates and formamidines.

At least one carbamate of the general formula:

R2 N=CH-N/ w R4 R3 :O( ,-NHR

wherein R and R each represents an alkyl radical containing up to 4 carbon atoms, or R stands for hydrogen and R an alkyl radical with up to 4 carbon atoms, and their salts, have good acaricidal and especially 'acaricidal/ ovicidal properties, to form preparations having a potential effect on vegetable and animal parasites.

Preparations having insecticidal and acaricidal activities are described in British specification 987,381, which contain carbamates of the general formula:

wherein R represents an alkyl or cyclohexyl radical, R and R each represents an alkyl radical or R +R together with the nitrogen atom a ring which may contain further hetero atoms, and R and R each represents a hydrogen or halogen atom or an alkyl or alkenyl radical.

It is also known from British specification 1,039,930 that preparations containing formamidines of the general formula:

wherein R and R each represents an alkyl radical containing up to 4 carbon atoms, or R stands for hydrogen and R an alkyl radical with up to 4 carbon atoms, and their salts, have good acaricidal and especially acaricidal/ ovicidal properties.

The present invention is based on the observation that synergistic pesticidal preparations have been produced that contain at least one carbamate of the above general formula (1) in admixture with at least one formamidine (2) of the above general formula. Such preparations produce a synergistic combination having a greater effect upon vegetable and animal parasites than the cumulative effect of the single components used per se.

This activity, which surpasses the activity of the single components substantially, is surprising and could not have been foreseen since at this stage it is not possible to make any predictions in the absence of knowledge of the mechanism on which this activity depends.

The use of the new combined mixtures of this invention offers substantial advantages since, to achieve an equivalent eifect against many pests, a smaller quantity of active substance is needed than when the components are used singly. Therefore, pests can be controlled in a more successful, safe and economic manner and it is possible, for example, to reduce substantially the waiting periods between treatment and harvesting.

A special advantage of the mixtures of this invention is their increased effect upon all development stages of mites that appear as parasites on plants and animals since this is the only way of controlling them successfully. This effect is unexpected because with all known acaricides, the main effect is found either only against the mobile stages of the pests, i.e., adulticidal effect, or against their ova and in most cases also their larvae, i.e., ovicidal effect. A mite population of, for example, species of the Tetranychidae family consists always of various stages of development, and mobile stages are always found side by side with ova so that it is often possible for new generations of the pests to emerge after a short time either from the undamaged ova or from the mobile stages.

The mixtures of this invention not only overcome the said disadvantage of the known acaricides, but in addition, they have a more potent effect against both stages, and this constitutes an appreciable technical advantage.

Moreover, it has been observed that the mixtures of this invention are also superior in their effect as acaricides and/or acaricides/ovicides to known acaricides, as is revealed by the comparative tests shown below.

The single components to be used in the mixtures of this invention are primarily the following active substances or their salts with inorganic or organic acids:

A.OARBAMATES No. Compound Physical Constant 1.. 3-rlimethylami110mothyleniminophenyl-N- M.P. 102-103 C.

rncthylcarbamate.

2 4-dirnctilylaminomethyleniminophenyl-N- M.P. 8285 C.

methylcarbamate.

3 4dimethylaminomethylenimino-3-methyl- M.P 110 C phenyl-N-methylcarb amate.

4 4-dlethylaminomethylenimino-3-methyl- M.P. 178179 O phenyl-N-methylcarbamatc.

5 4-dlmethylaminomethylenimino-3-methyl- Oil.

phenyLN-ethylcarbamate.

6 4-dlmethylaminomethylenimino-2-allyl- M.P. 120121 O phenyl-N-methylearbamate.

7- 4-d1methylaminomethylenimino-B,5-di- M.P. 156-157 C.

methylphenyl-N-methylcarb amate.

8 4-diethylaminomethylenimino-3,5-di- M.P. 8687 C.

rnethylphenyl-Nmethylcarbamate.

9 4-d1methylaminomethy1enimino-3methyl- M. P. 127.5-128" O 6 1sopropylpl1cnyl-N -methylcarbamate.

10 4-diethylaminornethylenimino-3-methyl'6- M .1. 9292.5 C

isopropylphenyl-Nanethylcarbam ate.

11 4-diethylaminomethylenimino-2-methyl-5- isopropylphenyl-N-methylcarbamate.

12 4-dirncthylaminomethylenimino-3-metl1yl- 5-isop1op ylphonyl-N-methylcarbamate.

l3 l-dietllylaminomethyleninrino-S-1uothyl-5- Oil. isopropylphenyl-N-methylcarbamate.

14".- -(N,N-tetramethylenan1inomcthyleninr- M.P. 185 C.

1no%-3,5-di1nethylphcnyl-N-rnctliylcaibama e.

15 4-(N,N-pcntamctliylenaminomctliylcnim- M.P. 85.U C.

1no?c-3,5-di1nothylphcnyl-N-niothylcarbama e.

16".. 4-morpholinomethylenimino-3,5-diniethyl- M.P. 144-145 C.

phenyLN-methylcarbamate.

17 3-dimethylaminomethylenimino-4-methyl- M.P. 118119 C.

phenyl-N-methylcarbamate.

18 S-dimethylaminomethyleniminophenyl-N- M.P. til-65 C.

butylcarbamate.

l9- 4-dimethylaminometliyleniminophenyl-2- chlorop henyLN-methylcarbamate.

20 4-dimethylaminomethylenimino-3-methylp henyl-N-cyclohexylcarb amate.

M.P. 118ll9 C3 M.P. 100-103 O.

21- 4-dlglefhygrmingmethyleniminophenyl-N- M.P. 105108 O.

c y car ama e.

22- -tirrtrleghylgmingmethyleniminophenyl-N- Oil no 1.5450.

n y car ama e.

23 4-dimethylaminomethyleniminophcnyl-3,5- M.P. 146 147 C drmethylp henyl-N-ethylcarbamato.

l Hydrochloride. 2 Chloracetate.

and their salts.

13 .F0 RMAMIDINES 2 N-(2-methyl-4-chlorophenyl) -N ,Ndimethylformamidine.

3 N-gimebhyl-tehlorophenyl) -N,N-dimethylformamidinium 4- N-(2-methyl-4-0l1l0r0phenyl) -N,N-diethylforman1idine.

5 N (2-methyl-4-chlorophenyl) -N '-nropylformamidine.

G N-(2-methyl4-chlorophenyl) -N ,N -di-n-propylformamidine.

7 N(2metliyll-chlorophenyl) -N-isobutylformamidine.

8 N-(2-methyl-4-eh1orophonyl) -Nsec0nda1'y butylformamidine.

and their salts.

The mixtures of this invention may be applied as such or in conjunction or admixture with other pesticides, such as insecticides, acaricides or fungicides. The preparations take the usual form of plant protection preparations containing liquid or solid vehicles. Suitable liquid vehicles are, inter alia, water, mineral oils or solvents; suitable solid vehicles are, for example, bentonite, bleaching earth, gypsum, lime, kieselguhr, pyrophillite, silica or talcum. The preparations may also contain further additives such as emulsifiers, wetting or binding agents, propellant gases, aromas, stabilizers, pest attracting sub stances or repellants. The preparations may be used, inter alia, as dusting or casting agents or granulates, as sprayed, sprinkled or atomized liquids, as aerosols or fumigants.

The amount of the mixtures of this invention to be infor example, in insecticides, acaricides or the like, may vary within wide limits and depends among others on the ratio of the components, on the type of preparation, on the manner of application, the desired control effect and on the kind of pest to be controlled. Depending on the form of application, the concentration of the mixture in the preparation may be from about 0.1 to by weight calculated from the weight of the preparation as a whole, and the preparation may be used in concentrations down to 0.001% by weight. In general, however, working concentrations between about 0.025 and 10% in liquid or solid vehicles produce excellent results. For some purposes, a working concentration up to about 25% by weight may be desirable.

In the mixtures of this invention, the weight ratio of the carbamate A to the formamidine B above may as a rule vary from about 1 to 5: about 1 to 10.

Particularly good results are achieved with a weight ratio of carbamate A: formamidine B=121 to 1:2.

The compounds contained in the new mixtures of this invention may be used as such or in the form of their salts, for example, of the water-soluble hydrochlorides.

These compounds which, as mentioned above, are as such known, may be prepared in a manner known in the art.

The mixtures of this invention, which contain the active substances, are prepared in the usual manner in mills, mixers or the like.

Among the above-mentioned components of the mixtures of this invention, the following active substances have proved particularly valuable for controlling plant parasites (mites): 3-dimethylaminomethylenimino-phenyl- N-methylcarbamate and 4-dimethylaminomethylenirnino- 3-methylphenyl-N-methylcarbamate (Compounds A1 and A3) and N (2. methyl-4-chlorophenyl)-N',N'-dimethylformamidine, Compound B-2, and their salts, especially the hydrochlorides. A preferred ratio carbamate A-l: formarnidine B2, or their salts, is 1:2 and the ratio carbamate A3: formamidine B-2, or their salts, is 1:1.

It is another advantage of the mixtures to be used according to this invention that they act against insects and other pests as well as against their ova so that they tend themselves to a wide variety of uses.

As examples of pests that can be controlled with good results, the following may be mentioned: Codling moth (Carpocapsa pomonella); peach borer (Cydia molesta); peach moth (Anarsia lineatella); summer fruit tortrix moth (Capua reticulana); prune saw fly (Hoplocampa hapla and minuta); apple flea (Paylla mali); aphids (Empoasca sp.); San Jos scale (Quadraspidiotus perniciosus); moths (Leucoptera sctitella and Litlzocolletis blancardella) The unexpected superiority of the mixtures of this invention compared with the single components is revealed by the following experiments:

EXAMPLE 1 In 7 field tests with numerous repetitions in apple cultures to control the fruit tree ermine moth (Metatetranychus ulmi Koch), the following results were recorded; in these evaluations the mixed products were accorded the value of and the effects of the single components are shown as percentages thereof. The preparations tested contained 3 dimethylaminomethyleniminophenyl N- methylcarbamate (A-1) and N-(2-methyl-4-chlorophenyl)-N,N'-dimethylformamidine (B2) in the weight ratio 0 of 1:2, or 4-dimethylaminomethylenimino-3-methylphenyl N methylcarbamate (A-3) and N (2 methyl 4- chlorophenyl) N',N dimethylformamidine (B-2) in the weight ratio of 1:1, and the results obtained were corporated in pesticidal and plant protecting preparations, 75 compared with those obtained with preparations containing the single components. The preparations were applied in the form of aqueous suspensions.

Active substance in At the Weight 100 liters of Evaluation of Preparation ratio of spray broth effect contains AzB in grams achieved EXAMPLE 2 The following table gives the LD values of the preparations of this invention and of a few known acaricides. These values were determined by tests, using round pieces of bean leaves blanked out (18 mm. diameter) from the leaves, which were placed upside down on a sheet of foam material in Petri dishes fiiled with water, and each piece was infested with female spider mites. For the ovicidal tests, the ova were obtained by leaving the female mites for 24 hours on the test pieces and then removing them. The mites and their ova were treated with 4 mg. of spray broth per cm. using in each case 3 to 4 concentration steps within the anticipated LD range. In the adulticide tests, 4 pieces of leaves infested with a total of 40 adults, and for the ovicide tests, 3 pieces of leaves infested with about 200 ova were used, and the mortality values were calculated after 3 to 4, and 7 days respectively in percent of the killed mites to the total sum of mites used in the test and plotted on socalled Log-Probit paper (probability ordinates and abscissae). Through each point, a straight line was drawn and the values of the 50% mortality in percent of active substance were read off.

The superiority of the preparations of this invention, which contain 3 dimethylaminomethyleniminophenyl-N- methyl-carbamate (Al) or 4-dimethylaminomethylenirnino 3 methyl phenyl N methylcarbamate (A-3), in each case in admixture with N-(2-methyl-4-chlorophenyl)N',N-dimethylformarnidine (B2) at a weight ratio of 1:2 and 1:1 respectively, is unambiguous since, in contradistinction to the reference preparations, an approximately equal effect is achieved upon all stages of the pests.

LD50 in parts per million Ovicide/ Weight Adultov0lar- Preparation contains ratio icide vicide Mixture of this invention' 2. 9 21. 4 8 ca 40 62 6. 7 Reference preparations:

0,0-dimethyl-S-Z-(ethylsulphiuyD- ethylthiophosphate O. 24 0,0-dimethyl-N-methylcarbamoylmethyldithiophosphate 2. 3 27 0,0-dimethyldiethylamido-1- chloro-erotonylphosphate 3. 7 200 0,0-diethyl-2-isopropyl 4-methyl- 6-pyrimidinyl-thiophosphate 14 ca 400 0,0-diethyl-p-nitrophenylthiophosphate 13. 7 310 1,1-bis-(p-chlorophenyl)-2,2,2-

triehlorethane 19 82 2,4,5,4-tetrachlorodiphenylsulphone. 2, 000 1. 2 p-Chlorophenyl-p-chlorobe11- zenesulphonate 2, 000 2 0 What We claim is:

1. A pesticidal preparation comprising a 1:2 weight ratio of 3 dimethylaminomethyleniminophenyl N methyl carbamate and N (2 methyl 4 chlorophenyl)- N ,N dimethylformamidine.

2. A pesticidal preparation comprising a 1:1 weight ratio of 4 dimethylaminomethylenimino 3 methylphenyl N methyl carbamate and N (2 methyl 4 chlorophenyl)-N ,N dimethylformamidine.

3. A method of controlling fruit tree ermine moths and spider mites comprising applying a pesticidal effective amount of the composition of claim 1 to said moths and mites.

4. A method of controlling fruit tree ermine moths and spider mites comprising applying a pesticidal effective amount of the composition of claim 2 to said moths and mites.

References Cited UNITED STATES PATENTS 3,284,289 11/1966 Duerr et al. 16730 3,336,186 8/1967 Peissker et al. 167-30 ALBERT T. MEYERS, Primary Examiner FREDERICK E. WADDELL, Assistant Examiner US. Cl. X.R. 424-326, 330 

